WO2021091830A1 - Titanated catalysts, methods of preparing titanated catalysts, and methods of epoxidation - Google Patents
Titanated catalysts, methods of preparing titanated catalysts, and methods of epoxidation Download PDFInfo
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- WO2021091830A1 WO2021091830A1 PCT/US2020/058563 US2020058563W WO2021091830A1 WO 2021091830 A1 WO2021091830 A1 WO 2021091830A1 US 2020058563 W US2020058563 W US 2020058563W WO 2021091830 A1 WO2021091830 A1 WO 2021091830A1
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- Prior art keywords
- silica support
- silica
- titanium
- olefin
- support
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- 238000000034 method Methods 0.000 title claims abstract description 88
- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- 238000006735 epoxidation reaction Methods 0.000 title claims abstract description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 492
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 237
- 150000001336 alkenes Chemical class 0.000 claims abstract description 47
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000011324 bead Substances 0.000 claims abstract description 38
- 239000007800 oxidant agent Substances 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 50
- 239000010936 titanium Substances 0.000 claims description 50
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 47
- 239000011148 porous material Substances 0.000 claims description 29
- NMNOLZYZNVYLRJ-UHFFFAOYSA-N 3-hydroperoxyhexane Chemical compound CCCC(CC)OO NMNOLZYZNVYLRJ-UHFFFAOYSA-N 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910001868 water Inorganic materials 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 7
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 6
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 150000003609 titanium compounds Chemical class 0.000 claims description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 3
- MRIZMKJLUDDMHF-UHFFFAOYSA-N cumene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1 MRIZMKJLUDDMHF-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 description 20
- 230000008569 process Effects 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229910052814 silicon oxide Inorganic materials 0.000 description 9
- 239000002245 particle Substances 0.000 description 6
- -1 titanium alkoxides Chemical class 0.000 description 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 101100168884 Drosophila melanogaster alpha-Cat gene Proteins 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910010165 TiCu Inorganic materials 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- KZCYIWWNWWRLBQ-UHFFFAOYSA-P diazanium 3-methanidylbutan-2-one titanium(2+) dihydrate Chemical compound [NH4+].[NH4+].O.O.[Ti++].CC([CH2-])C([CH2-])=O.CC([CH2-])C([CH2-])=O KZCYIWWNWWRLBQ-UHFFFAOYSA-P 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 150000002432 hydroperoxides Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052756 noble gas Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000004846 x-ray emission Methods 0.000 description 2
- GQNOPVSQPBUJKQ-UHFFFAOYSA-N 1-hydroperoxyethylbenzene Chemical compound OOC(C)C1=CC=CC=C1 GQNOPVSQPBUJKQ-UHFFFAOYSA-N 0.000 description 1
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical compound CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 102220500397 Neutral and basic amino acid transport protein rBAT_M41T_mutation Human genes 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-M hydroperoxide group Chemical group [O-]O MHAJPDPJQMAIIY-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000001282 organosilanes Chemical group 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
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- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0209—Impregnation involving a reaction between the support and a fluid
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0238—Impregnation, coating or precipitation via the gaseous phase-sublimation
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/08—Epoxidation
Definitions
- U.S. Patent Application Publication No. 2015/01822959 which is incorporated herein by reference, discloses a process for preparing a titanium catalyst system for epoxidation reactions that includes (i) impregnating a silica carrier with a liquid solution of a titanium compound in an inorganic solvent system, (ii) drying the carrier, (iii) calcinating (i.e., “calcining”) the dried product, and (iv) silylating the calcinated (i.e., “calcined”) product.
- the method may also include calcinating the titanium-treated silica support to form a calcinated titanium-treated silica support; contacting the calcinated titanium-treated silica support with water vapor; and silylating the calcinated titanium- treated silica support to form the titanated silica catalyst.
- a titanium-treated silica support is washed with a solvent.
- silylating agent is an organodisilazane of the following formula:
- the silica support includes an inorganic siliceous solid, such as silicon oxide.
- the siliceous solid is an amorphous silicon oxide.
- the silica support is porous. A silica support is porous when it includes one or more pores and/or interstices within its structure.
- the silica support has a relatively high average pore volume, e.g., greater than 1.25 g/cm 3 .
- the average pore volume of the silica support is about 1.25 g/cm 3 to about 3.50 g/cm 3 .
- the average pore volume of the silica support is about 1.5 g/cm 3 to about 3.0 g/cm 3 .
- the average pore volume of the silica support is about 2.0 g/cm 3 to about 2.5 g/cm 3 .
- the average pore volume of the silica support is about 2.20 g/cm 3 to about 2.5 g/cm 3 .
- the average pore volume of the silica support is greater than 2.0 g/cm 3 .
- the average pore volume and/or average surface area of a silica support may be measured using nitrogen porosimetry.
- the average pore diameter of the silica support is about 70 A to about 150 A. In some embodiments, the average pore diameter of the silica support is about 90 A to about 110 A. In some embodiments, the average pore diameter of the silica support is about 91 A to about 108 A.
- the silica support may have any desired particle size.
- a desired particle size of the silica support is obtained through crushing and/or extruding.
- a desired particle size of the silica support is obtained by classifying the silica support through a sieve.
- the average diameter of the silica support is less than 5.0 mm.
- the average diameter of the silica support is from about 0. lmm to about 5.0 mm.
- the average diameter of the silica support is from about 0.2 mm to about 4 mm.
- the silica support is dried before the silica support is contacted with a liquid.
- the drying of the silica support includes heating the silica support to a temperature of about 100° C to about 850° C. In some embodiments, the temperature is greater than 120° C. In some embodiments, the temperature may be in the range of from about 150° C to about 300° C.
- the silica support is dried in a vacuum. In some embodiments, the silica support is dried under a flowing stream of an inter gas, such as nitrogen or a noble gas. In some embodiments, the silica support is dried for a time of about from 1 hour to about 48 hours. In some embodiments, the silica support is dried for a time of from about
- any olefin may be used in the methods of epoxidation described herein.
- the term “olefin” may refer to any hydrocarbyl, such as a C1-C30 hydrocarbyl, that includes at least one non-aromatic double bond.
- the olefin has 1 to 24 carbon atoms.
- the olefin has 1 to 12 carbon atoms.
- the olefin is propylene, 1-octene, or a combination thereof.
- the olefin is substituted with one or more other functional groups, such as a hydroxyl or halide.
- any ratio of olefin to oxidant may be used in the methods of epoxidation described herein.
- the molar ratio of olefin to oxidizing agent is from about 1:1 to about 20:1, or about 10:1 to about 12:1.
- the methods of epoxidation described herein may be modified by adjusting the pressure and/or the temperature.
- the methods of epoxidation are carried out, at least in part, at a temperature within the range of from about 25° C to about 200° C.
- the temperature is within the range of from about 50° C to about 160° C.
- the temperature is within the range of from about 70° C to about 140° C.
- the methods of epoxidation are carried out, at least in part, at a pressure that is from about ambient pressure to greater than atmospheric pressure.
- the pressure is within the range of from about 20 psi to about 1500 psi.
- propylene used as the olefin, and the pressure is within the range of from about 400 psi to about 1000 psi.
- the first silica support included AlphaCat ® 4000 silica particles (PQ Corporation, USA), which are spherical particles having an average particle diameter of about 2 mm to about 3 mm, a surface area of about 455 m 2 /g, and a pore volume of about 1.06 cc/g.
- the second silica support included AlphaCat ® 4000 silica particles (PQ Corporation, USA), which are spherical particles having an average diameter of about 2 mm to about 3 mm, a surface area of about 533 m 2 /g, and a pore volume of about 1.2 cc/g.
- AlphaCat ® 4000 silica particles of this example was tested in an octene/l-ethylbutyl hydroperoxide epoxidation process.
- the octene epoxidation tests were performed using a POSM oxidizer effluent ( ⁇ 7 - 9 % EBHP in ethylbenzene, EB) washed with caustic and treated with CO2/H2O to remove sodium.
- the testing temperature was 70°C for 3 hours using 0.05 g catalyst in a mixture of 1 mL octene and 5 mL POSM oxidate.
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| CN202080075021.3A CN114630710B (zh) | 2019-11-04 | 2020-11-02 | 钛酸盐化催化剂，制备钛酸盐化催化剂的方法，和环氧化的方法 |
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| US1748408A (en) | 1927-03-14 | 1930-02-25 | Chalon E Bridwell | Boat |
| WO2001097967A1 (en) * | 2000-06-21 | 2001-12-27 | Shell Internationale Research Maatschappij B.V. | Catalyst composition, process for its preparation and use thereof |
| US20150182959A1 (en) | 2013-12-30 | 2015-07-02 | Shell Oil Company | Relating to epoxidation catalysts |
| WO2017080962A1 (en) | 2015-11-09 | 2017-05-18 | Shell Internationale Research Maatschappij B.V. | Catalyst preparation |
| US10017484B2 (en) | 2015-12-02 | 2018-07-10 | Lyondell Chemical Technology, L.P. | Catalysts containing specific titanium polymorphic forms |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US1748408A (en) | 1927-03-14 | 1930-02-25 | Chalon E Bridwell | Boat |
| WO2001097967A1 (en) * | 2000-06-21 | 2001-12-27 | Shell Internationale Research Maatschappij B.V. | Catalyst composition, process for its preparation and use thereof |
| US20150182959A1 (en) | 2013-12-30 | 2015-07-02 | Shell Oil Company | Relating to epoxidation catalysts |
| WO2017080962A1 (en) | 2015-11-09 | 2017-05-18 | Shell Internationale Research Maatschappij B.V. | Catalyst preparation |
| US10017484B2 (en) | 2015-12-02 | 2018-07-10 | Lyondell Chemical Technology, L.P. | Catalysts containing specific titanium polymorphic forms |
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| EP4054759A1 (de) | 2022-09-14 |
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